Nanometer reinforced impact modifier for polyvinyl chloride and its preparation method

Abstract

The application discloses a kind of nano-reinforced impact modifier for polyvinyl chloride and preparation method thereof, it is related to impact modifier technical field.The raw materials of the nano-reinforced impact modifier include CNC@ACM complex, hyperbranched polyglycidol, amino-terminated hyperbranched polyamide, organically modified montmorillonite, maleic anhydride grafted POE, silane coupling agent, nano zinc oxide;The CNC@ACM complex is prepared from acrylate rubber, silanized nanocellulose and p-toluenesulfonic acid;The preparation method of the nano-reinforced impact modifier includes nanocellulose pretreatment, synthesis of CNC@ACM complex, auxiliary component pretreatment, preparation of base material, and preparation of the nano-reinforced impact modifier steps.The nano-reinforced impact modifier prepared by the application can effectively enhance the mechanical properties and thermal properties of polyvinyl chloride.

Description

Technical Field

[0001] This invention relates to the field of impact modifier technology, specifically to a nano-reinforced impact modifier for polyvinyl chloride and its preparation method. Background Technology

[0002] Polyvinyl chloride (PVC) is a widely produced and used general-purpose plastic, characterized by low cost, excellent chemical resistance, and balanced mechanical properties. It is extensively used in building materials, packaging products, and electronics. However, the presence of numerous chlorine atoms in the PVC molecular chain and strong intermolecular forces result in significant low-temperature brittleness and low notched impact strength, limiting its application in high-impact environments. To address this deficiency, impact modifiers have become indispensable additives in PVC processing. These modifiers form an elastic dispersed phase within the PVC matrix, absorbing impact energy and inhibiting crack propagation, thereby improving the material's toughness.

[0003] Commonly used impact modifiers for polyvinyl chloride (PVC) include acrylate rubbers, chlorinated polyethylene, and methyl methacrylate-butadiene-styrene copolymers. Among these, acrylate rubbers are widely used due to their good compatibility with PVC and excellent weather resistance; however, adding them alone can easily lead to a decrease in material rigidity. Furthermore, existing modifiers often struggle to balance impact resistance and rigidity, and during high-temperature processing, insufficient interfacial compatibility can cause a decrease in the thermal stability of the composite material, failing to meet the comprehensive performance requirements of high-end PVC materials. Prior art, disclosed in CN118048043B, describes a high tensile strength impact modifier for PVC and its preparation method. This prior art mainly relies on nitrile rubber coated with lignin and modified nanoparticles, offering limited improvement to the mechanical properties of PVC, insufficient balance between rigidity and toughness, and performance degradation during high-temperature processing. The prior art disclosed in CN119875022A is a transparent impact modifier for polyvinyl chloride with yellowing resistance and its preparation method. The core of this prior art is to improve yellowing resistance and impact resistance. The overall mechanical property improvement is limited to toughness only, and the effect on maintaining the thermal properties of polyvinyl chloride at high temperatures is poor.

[0004] In summary, although the existing technical solutions have improved some properties of impact modifiers to a certain extent, the following technical problems still exist: the improvement of the mechanical and thermal properties of polyvinyl chloride is limited. Summary of the Invention

[0005] In order to solve the above-mentioned problems in the prior art, the present invention provides a nano-reinforced impact modifier for polyvinyl chloride and its preparation method, and achieves the following objective: to prepare a nano-reinforced impact modifier that can effectively enhance the mechanical and thermal properties of polyvinyl chloride.

[0006] To achieve the above objectives, the following technical solution is adopted:

[0007] A nano-reinforced impact modifier for polyvinyl chloride, comprising, by weight: 55-60 parts of CNC@ACM composite, 6-8 parts of hyperbranched polyglycidyl ether, 6-8 parts of amino-terminated hyperbranched polyamide, 4-6 parts of organo-modified montmorillonite, 4-5 parts of maleic anhydride-grafted POE, 0.6-0.8 parts of silane coupling agent, and 2-3 parts of nano-zinc oxide.

[0008] The CNC@ACM composite is prepared from acrylate rubber, silanized nanocellulose, and p-toluenesulfonic acid.

[0009] The hyperbranched polyglycidyl has a molecular weight of 800-2500 g / mol.

[0010] The terminal amino hyperbranched polyamide has a terminal amino functionality of 4-14 and a molecular weight of 300-1400 g / mol.

[0011] The grafting rate of maleic anhydride-grafted POE is 1.0%-1.5%.

[0012] The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0013] This invention also provides a method for preparing a nano-reinforced impact modifier for polyvinyl chloride, comprising the following steps:

[0014] Step 1: Pretreatment of nanocellulose

[0015] Dry nanocellulose was added to toluene at a mass ratio of 1:(19-20) and ultrasonically dispersed for 30-40 min at a power of 300-400 W. A silanizing agent was added at a mass ratio of (0.3-0.5):1, and the mixture was protected under nitrogen atmosphere and heated to 110-115℃ for 6-8 h. The mixture was then cooled to room temperature and centrifuged at 6000-7000 rpm for 15-20 min, collecting the solid phase. After centrifugation, the solid phase was washed 3-5 times with anhydrous ethanol and then dried at 50-60℃ for 8-10 h to obtain silanized nanocellulose. The nanocellulose had a diameter of 5-100 nm and a length of 50-350 nm. The silanizing agent was a mixture of methyltrimethoxysilane and triethylamine, where the triethylamine was 8% of the mass of methyltrimethoxysilane.

[0016] Step 2: Synthesize the CNC@ACM complex

[0017] Silanized cellulose nanoparticles were dispersed in toluene at a mass ratio of 1:(9-10) and subjected to ultrasonic treatment at a power of 200-300W for 30-40 minutes. After ultrasonication, acrylate rubber was added and stirred until fully dispersed at a mass ratio of (6-7):1. Then, p-toluenesulfonic acid was added at a mass of 1.5-2% of the mass of silanized cellulose nanoparticles. The temperature was raised to 110-115℃, and the stirring rate was 300-400 rpm for 6-7 hours. After the reaction was completed, the mixture was cooled to room temperature, and excess ethanol was added and stirred until all the solid precipitated. The mixture was then centrifuged at 5000-6000 rpm for 10-15 minutes, and the solid phase was collected. The solid phase was washed 3-5 times with ethanol and then dried at 60-70℃ for 8-9 hours to obtain the cellulose nanoparticle-coated acrylate rubber composite (CNC@ACM composite). The acrylate rubber selected is model AR200.

[0018] Step 3: Pretreatment of auxiliary components

[0019] Organized montmorillonite was dispersed in deionized water at a mass ratio of (1-2):40, and subjected to ultrasonic treatment at a power of 300-400W for 20-30 minutes. Then, it was stirred for 10-15 minutes at a stirring speed of 300-400 rpm to obtain an organized montmorillonite dispersion. Nano-zinc oxide was added to deionized water at a mass ratio of 1:10, and subjected to ultrasonic treatment at a power of 300-400W for 20-30 minutes to obtain a zinc oxide suspension. Silane coupling agent, ethanol, and deionized water were mixed at a mass ratio of 1:4:0.2, heated to 40-45℃, and reacted for 30-40 minutes to obtain a pre-hydrolyzed silane solution.

[0020] Step 4: Preparation of base materials

[0021] The CNC@ACM complex was mixed with sodium lauryl sulfate and deionized water and stirred. The mass ratio of CNC@ACM complex, sodium lauryl sulfate and deionized water was 1:(0.2-0.3):(9-10). The mixture was stirred for 10-15 minutes at a stirring speed of 300-400 rpm. Hyperbranched polyglycidyl ether was added, the temperature was raised to 50-55℃, the stirring speed was increased to 400-500 rpm, and the reaction was stirred for 40-50 minutes. Then, amino-terminated hyperbranched polyamide was added, the temperature was raised to 60-65℃, and the reaction was continued for 40-50 minutes to obtain the base material.

[0022] Step 5: Prepare nano-reinforced impact modifier

[0023] Maleic anhydride-grafted POE was mixed with toluene, sodium lauryl sulfate, and glycerol in a mass ratio of 2:(10-15):(0.8-1):(2.5-3) to obtain a maleic anhydride-grafted POE pretreatment solution.

[0024] Add organo-modified montmorillonite dispersion and pre-hydrolyzed silane solution to the base material, stir evenly, and then sonicate at 400-500W for 40-50 minutes. Add zinc oxide suspension, control the temperature at 50-60℃, stir at 300-400 rpm, and react for 1-1.5 hours. Raise the temperature to 60-70℃, slowly add maleic anhydride-grafted POE pretreatment solution, and then stir for 1.5-2 hours. After the reaction is complete, centrifuge at 8000-9000 rpm for 20-30 minutes and collect the solid product. Wash the solid product 3-4 times with anhydrous ethanol, and then dry at 60-70℃ for 12-14 hours. After drying, grind with a high-speed pulverizer and pass through a 200-mesh sieve to obtain the nano-reinforced impact modifier.

[0025] The beneficial effects of this invention are as follows:

[0026] (1) The present invention provides a nano-reinforced impact modifier for polyvinyl chloride (PVC), which effectively improves the mechanical properties of PVC. The notched impact strength of the PVC test samples at 23°C reached 64.5-67.2 KJ / m. 2 The tensile strength is 66.3-68.6 MPa, the elongation at break is 372-384%, and the flexural strength reaches 84.8-87.5 MPa.

[0027] (2) The nano-reinforced impact modifier for polyvinyl chloride of the present invention has a significant enhancing effect on the thermal properties of polyvinyl chloride. The Congo red test paper color change time of the polyvinyl chloride test sample is 82-86 min, and the Vicat softening point is 88.1-89.5℃. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of the present invention clearer, the embodiments of the present invention will be described in further detail below. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0029] Example 1: A nano-reinforced impact modifier for polyvinyl chloride and its preparation method

[0030] A nano-reinforced impact modifier for polyvinyl chloride, comprising, by weight, the following raw materials: 55 parts CNC@ACM composite, 8 parts hyperbranched polyglycidyl ether, 8 parts amino-terminated hyperbranched polyamide, 4 parts organo-modified montmorillonite, 4 parts maleic anhydride-grafted POE, 0.6 parts silane coupling agent, and 2 parts nano zinc oxide.

[0031] The hyperbranched polyglycidyl has a molecular weight of 800-2500 g / mol.

[0032] The terminal amino hyperbranched polyamide has a terminal amino functionality of 4-14 and a molecular weight of 300-1400 g / mol.

[0033] The grafting rate of maleic anhydride-grafted POE is 1.0%-1.5%.

[0034] The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0035] The organic montmorillonite used is of the Nanomer type. ® I.44P.

[0036] A method for preparing a nano-reinforced impact modifier for polyvinyl chloride includes the following steps:

[0037] Step 1: Pretreatment of nanocellulose

[0038] Dry nanocellulose was added to toluene at a mass ratio of 1:19 and ultrasonically dispersed for 30 min at 400 W. A silanizing reagent was then added at a mass ratio of 0.3:1 to nanocellulose. The mixture was protected under nitrogen atmosphere and heated to 110 °C for 8 h. After cooling to room temperature, the mixture was centrifuged at 6000 rpm for 20 min, and the solid phase was collected. After centrifugation, the solid phase was washed three times with anhydrous ethanol and then dried at 50 °C for 10 h to obtain silanized nanocellulose. The silanizing reagent was a mixture of methyltrimethoxysilane and triethylamine, where the triethylamine was 8% of the mass of methyltrimethoxysilane.

[0039] Step 2: Synthesize the CNC@ACM complex

[0040] Silanized cellulose nanoparticles were dispersed in toluene at a mass ratio of 1:9 and subjected to ultrasonic treatment at a power of 200W for 40 min. After ultrasonication, acrylate rubber was added and stirred until fully dispersed at a mass ratio of 6:1 to silanized cellulose nanoparticles. Then, p-toluenesulfonic acid was added at a concentration of 1.5% of the mass of silanized cellulose nanoparticles. The mixture was heated to 110°C and stirred at 300 rpm for 7 h. After the reaction was completed, the mixture was cooled to room temperature, and excess ethanol was added and stirred until all the solid precipitated. The mixture was then centrifuged at 5000 rpm for 15 min, and the solid phase was collected. The solid phase was washed three times with ethanol and then dried at 60°C for 9 h to obtain the CNC@ACM composite. The acrylate rubber used was model AR200.

[0041] Step 3: Pretreatment of auxiliary components

[0042] Organo-modified montmorillonite was dispersed in deionized water at a mass ratio of 1:40 and subjected to ultrasonic treatment at 300W for 30 min. Then, it was stirred for 10 min at 400 rpm to obtain an organo-modified montmorillonite dispersion. Nano-zinc oxide was added to deionized water at a mass ratio of 1:10 and subjected to ultrasonic treatment at 300W for 30 min to obtain a zinc oxide suspension. A silane coupling agent, ethanol, and deionized water were mixed at a mass ratio of 1:4:0.2, heated to 40℃, and reacted for 40 min to obtain a pre-hydrolyzed silane solution.

[0043] Step 4: Preparation of base materials

[0044] The CNC@ACM complex was mixed with sodium lauryl sulfate and deionized water in a mass ratio of 1:0.2:9. The mixture was stirred for 15 minutes at a speed of 300 rpm. Hyperbranched polyglycidyl glycerol was added, the temperature was raised to 50°C, the stirring speed was increased to 400 rpm, and the mixture was stirred for 50 minutes. Then, amino-terminated hyperbranched polyamide was added, the temperature was raised to 60°C, and the reaction was continued for 50 minutes to obtain the base material.

[0045] Step 5: Prepare nano-reinforced impact modifier

[0046] Maleic anhydride-grafted POE was mixed with toluene, sodium lauryl sulfate, and glycerol in a mass ratio of 2:10:0.8:2.5 to obtain a maleic anhydride-grafted POE pretreatment solution.

[0047] Organo-modified montmorillonite dispersion and pre-hydrolyzed silane solution were added to the base material and stirred evenly. Then, the mixture was ultrasonically treated at 400W for 50 minutes. Zinc oxide suspension was added, and the temperature was controlled at 50℃ with a stirring speed of 300 rpm for 1.5 hours. The temperature was raised to 60℃, and maleic anhydride-grafted POE pretreatment solution was slowly added dropwise, followed by stirring for 2 hours. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 30 minutes, and the solid product was collected. The solid product was washed three times with anhydrous ethanol and then dried at 60℃ for 14 hours. After drying, the product was ground using a high-speed pulverizer and passed through a 200-mesh sieve to obtain a nano-reinforced impact modifier.

[0048] Example 2: A nano-reinforced impact modifier for polyvinyl chloride and its preparation method

[0049] A nano-reinforced impact modifier for polyvinyl chloride, comprising, by weight: 58 parts CNC@ACM composite, 7 parts hyperbranched polyglycidyl ether, 7 parts amino-terminated hyperbranched polyamide, 5 parts organo-modified montmorillonite, 5 parts maleic anhydride-grafted POE, 0.8 parts silane coupling agent, and 3 parts nano zinc oxide.

[0050] The hyperbranched polyglycidyl has a molecular weight of 800-2500 g / mol.

[0051] The terminal amino hyperbranched polyamide has a terminal amino functionality of 4-14 and a molecular weight of 300-1400 g / mol.

[0052] The grafting rate of maleic anhydride-grafted POE is 1.0%-1.5%.

[0053] The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0054] The organic montmorillonite used is of the Nanomer type. ® I.44P.

[0055] A method for preparing a nano-reinforced impact modifier for polyvinyl chloride includes the following steps:

[0056] Step 1: Pretreatment of nanocellulose

[0057] Dry nanocellulose was added to toluene at a mass ratio of 1:20 and ultrasonically dispersed for 30 min at 400 W. A silanizing reagent was then added at a mass ratio of 0.4:1 to nanocellulose. The mixture was protected under nitrogen atmosphere and heated to 115 °C for 7 h. After cooling to room temperature, the mixture was centrifuged at 7000 rpm for 20 min, and the solid phase was collected. Following centrifugation, the solid phase was washed four times with anhydrous ethanol and then dried at 60 °C for 10 h to obtain silanized nanocellulose. The silanizing reagent was a mixture of methyltrimethoxysilane and triethylamine, where the triethylamine was 8% of the mass of methyltrimethoxysilane.

[0058] Step 2: Synthesize the CNC@ACM complex

[0059] Silanized cellulose nanoparticles were dispersed in toluene at a mass ratio of 1:10 and subjected to ultrasonic treatment at 300W for 40 min. After ultrasonication, acrylate rubber was added and stirred until fully dispersed at a mass ratio of 7:1 to silanized cellulose nanoparticles. Then, p-toluenesulfonic acid was added at 2% of the mass of silanized cellulose nanoparticles, and the mixture was heated to 115℃ with a stirring rate of 400 rpm for 7 h. After the reaction was completed, the mixture was cooled to room temperature, and excess ethanol was added and stirred until all the solid precipitated. The mixture was then centrifuged at 6000 rpm for 15 min, and the solid phase was collected. The solid phase was washed five times with ethanol and then dried at 70℃ for 9 h to obtain the CNC@ACM composite. The acrylate rubber used was model AR200.

[0060] Step 3: Pretreatment of auxiliary components

[0061] Organo-modified montmorillonite was dispersed in deionized water at a mass ratio of 1:40 and subjected to ultrasonic treatment at 400W for 20 min. Then, it was stirred for 15 min at 300 rpm to obtain an organo-modified montmorillonite dispersion. Nano-zinc oxide was added to deionized water at a mass ratio of 1:10 and subjected to ultrasonic treatment at 400W for 30 min to obtain a zinc oxide suspension. A silane coupling agent, ethanol, and deionized water were mixed at a mass ratio of 1:4:0.2, heated to 45℃, and reacted for 40 min to obtain a pre-hydrolyzed silane solution.

[0062] Step 4: Preparation of base materials

[0063] The CNC@ACM complex was mixed with sodium lauryl sulfate and deionized water in a mass ratio of 1:0.3:10. The mixture was stirred for 15 minutes at a speed of 400 rpm. Hyperbranched polyglycidyl glycerol was added, the temperature was raised to 55°C, the stirring speed was increased to 500 rpm, and the mixture was stirred for 50 minutes. Then, amino-terminated hyperbranched polyamide was added, the temperature was raised to 65°C, and the reaction was continued for 50 minutes to obtain the base material.

[0064] Step 5: Prepare nano-reinforced impact modifier

[0065] Maleic anhydride-grafted POE was mixed with toluene, sodium lauryl sulfate, and glycerol in a mass ratio of 2:15:0.9:3 to obtain a maleic anhydride-grafted POE pretreatment solution.

[0066] Organo-modified montmorillonite dispersion and pre-hydrolyzed silane solution were added to the base material and stirred evenly. Then, the mixture was ultrasonically treated at 500W for 40 minutes. Zinc oxide suspension was added, and the temperature was controlled at 60℃ with a stirring speed of 400 rpm for 1.5 hours. The temperature was raised to 70℃, and maleic anhydride-grafted POE pretreatment solution was slowly added dropwise, followed by stirring for 2 hours. After the reaction was completed, the mixture was centrifuged at 9000 rpm for 30 minutes, and the solid product was collected. The solid product was washed four times with anhydrous ethanol and then dried at 70℃ for 14 hours. After drying, the product was ground using a high-speed pulverizer and passed through a 200-mesh sieve to obtain a nano-reinforced impact modifier.

[0067] Example 3: A nano-reinforced impact modifier for polyvinyl chloride and its preparation method

[0068] A nano-reinforced impact modifier for polyvinyl chloride, comprising, by weight, 60 parts of CNC@ACM composite, 6 parts of hyperbranched polyglycidyl ether, 6 parts of amino-terminated hyperbranched polyamide, 6 parts of organo-modified montmorillonite, 5 parts of maleic anhydride-grafted POE, 0.8 parts of silane coupling agent, and 3 parts of nano-zinc oxide.

[0069] The hyperbranched polyglycidyl has a molecular weight of 800-2500 g / mol.

[0070] The terminal amino hyperbranched polyamide has a terminal amino functionality of 4-14 and a molecular weight of 300-1400 g / mol.

[0071] The grafting rate of maleic anhydride-grafted POE is 1.0%-1.5%.

[0072] The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0073] The organic montmorillonite used is of the Nanomer type. ® I.44P.

[0074] A method for preparing a nano-reinforced impact modifier for polyvinyl chloride includes the following steps:

[0075] Step 1: Pretreatment of nanocellulose

[0076] Dry nanocellulose was added to toluene at a mass ratio of 1:20 and ultrasonically dispersed for 40 min at 300 W. A silanizing reagent was then added at a mass ratio of 0.5:1 to nanocellulose. The mixture was protected under nitrogen atmosphere and heated to 115 °C for 6 h. After cooling to room temperature, the mixture was centrifuged at 7000 rpm for 15 min, and the solid phase was collected. After centrifugation, the solid phase was washed five times with anhydrous ethanol and then dried at 60 °C for 8 h to obtain silanized nanocellulose. The silanizing reagent was a mixture of methyltrimethoxysilane and triethylamine, where triethylamine accounted for 8% of the mass of methyltrimethoxysilane.

[0077] Step 2: Synthesize the CNC@ACM complex

[0078] Silanized cellulose nanoparticles were dispersed in toluene at a mass ratio of 1:10 and subjected to ultrasonic treatment at a power of 300W for 30 min. After ultrasonication, acrylate rubber was added and stirred until fully dispersed at a mass ratio of acrylate rubber to silanized cellulose nanoparticles of 7:1. Then, p-toluenesulfonic acid was added at a concentration of 2% of the mass of silanized cellulose nanoparticles. The mixture was heated to 115℃ and stirred at a rate of 400 rpm for 6 h. After the reaction was completed, the mixture was cooled to room temperature, and excess ethanol was added and stirred until all the solid precipitated. The mixture was then centrifuged at 6000 rpm for 10 min, and the solid phase was collected. The solid phase was washed five times with ethanol and then dried at 70℃ for 8 h to obtain the CNC@ACM composite. The acrylate rubber used was model AR200.

[0079] Step 3: Pretreatment of auxiliary components

[0080] Organomodified montmorillonite was dispersed in deionized water at a mass ratio of 1:20 and subjected to ultrasonic treatment at 400W for 20 min. Then, it was stirred for 15 min at 300 rpm to obtain an organomodified montmorillonite dispersion. Nano-zinc oxide was added to deionized water at a mass ratio of 1:10 and subjected to ultrasonic treatment at 400W for 20 min to obtain a zinc oxide suspension. A silane coupling agent, ethanol, and deionized water were mixed at a mass ratio of 1:4:0.2, heated to 45℃, and reacted for 30 min to obtain a pre-hydrolyzed silane solution.

[0081] Step 4: Preparation of base materials

[0082] The CNC@ACM complex was mixed with sodium lauryl sulfate and deionized water in a mass ratio of 1:0.3:10. The mixture was stirred for 10 minutes at a speed of 400 rpm. Hyperbranched polyglycidyl glycerol was added, the temperature was raised to 55°C, the stirring speed was increased to 500 rpm, and the mixture was stirred for 40 minutes. Then, amino-terminated hyperbranched polyamide was added, the temperature was raised to 65°C, and the reaction was continued for 40 minutes to obtain the base material.

[0083] Step 5: Prepare nano-reinforced impact modifier

[0084] Maleic anhydride-grafted POE was mixed with toluene, sodium lauryl sulfate, and glycerol in a mass ratio of 2:15:1:3 to obtain a maleic anhydride-grafted POE pretreatment solution.

[0085] Organo-modified montmorillonite dispersion and pre-hydrolyzed silane solution were added to the base material and stirred evenly. Then, the mixture was ultrasonically treated at 500W for 40 minutes. Zinc oxide suspension was added, and the temperature was controlled at 60℃ with a stirring speed of 400 rpm for 1 hour. The temperature was raised to 70℃, and maleic anhydride-grafted POE pretreatment solution was slowly added dropwise, followed by stirring for 1.5 hours. After the reaction was completed, the mixture was centrifuged at 9000 rpm for 20 minutes, and the solid product was collected. The solid product was washed four times with anhydrous ethanol and then dried at 70℃ for 12 hours. After drying, the product was ground using a high-speed pulverizer and passed through a 200-mesh sieve to obtain a nano-reinforced impact modifier.

[0086] Comparative Example 1

[0087] An impact modifier, by weight, comprises the following raw materials: 58 parts acrylate rubber, 7 parts hyperbranched polyglycidyl ether, 7 parts amino-terminated hyperbranched polyamide, 5 parts organo-modified montmorillonite, 5 parts maleic anhydride-grafted POE, 0.8 parts silane coupling agent, and 3 parts nano zinc oxide.

[0088] The hyperbranched polyglycidyl has a molecular weight of 800-2500 g / mol.

[0089] The terminal amino hyperbranched polyamide has a terminal amino functionality of 4-14 and a molecular weight of 300-1400 g / mol.

[0090] The grafting rate of maleic anhydride-grafted POE is 1.0%-1.5%.

[0091] The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0092] The acrylate rubber selected is model AR200.

[0093] The organic montmorillonite used is of the Nanomer type. ® I.44P.

[0094] A method for preparing an impact modifier includes the following steps:

[0095] Step 1: Pretreatment of auxiliary components

[0096] This step is the same as the "auxiliary component pretreatment" operation in Example 2.

[0097] Step 2: Preparation of base materials

[0098] Acrylic rubber was mixed with sodium lauryl sulfate and deionized water in a mass ratio of 1:0.3:10. The mixture was stirred for 15 minutes at a speed of 400 rpm. Hyperbranched polyglycidyl was added, the temperature was raised to 55°C, the stirring speed was increased to 500 rpm, and the mixture was stirred for 50 minutes. Then, amino-terminated hyperbranched polyamide was added, the temperature was raised to 65°C, and the mixture was stirred for another 50 minutes to obtain the base material.

[0099] Step 3: Prepare impact modifier

[0100] This step is the same as the "Preparation of Nano-Reinforced Impact Modifier" procedure in Example 2.

[0101] Comparative Example 2

[0102] An impact modifier, by weight, comprises: 58 parts of CNC@ACM complex, 7 parts of hyperbranched polyglycidyl ether, 7 parts of amino-terminated hyperbranched polyamide, 5 parts of maleic anhydride-grafted POE, 0.8 parts of silane coupling agent, and 3 parts of nano zinc oxide.

[0103] The hyperbranched polyglycidyl has a molecular weight of 800-2500 g / mol.

[0104] The terminal amino hyperbranched polyamide has a terminal amino functionality of 4-14 and a molecular weight of 300-1400 g / mol.

[0105] The grafting rate of maleic anhydride-grafted POE is 1.0%-1.5%.

[0106] The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0107] A method for preparing an impact modifier includes the following steps:

[0108] Step 1: Pretreatment of nanocellulose

[0109] This step is the same as the "nanocellulose pretreatment" operation in Example 2.

[0110] Step 2: Synthesize the CNC@ACM complex

[0111] This step is the same as the "Synthesis of CNC@ACM Complex" procedure in Example 2.

[0112] Step 3: Pretreatment of auxiliary components

[0113] Nano zinc oxide was added to deionized water at a mass ratio of 1:10 and subjected to ultrasonic treatment at a power of 300-400W for 20-30 minutes to obtain a zinc oxide suspension. Silane coupling agent, ethanol, and deionized water were mixed at a mass ratio of 1:4:0.2 and heated to 40-45℃ for 30-40 minutes to obtain a pre-hydrolyzed silane solution.

[0114] Step 4: Preparation of base materials

[0115] This step is the same as the "Basic Material Preparation" operation in Example 2.

[0116] Step 5: Prepare impact modifier

[0117] Maleic anhydride-grafted POE was mixed with toluene, sodium lauryl sulfate, and glycerol in a mass ratio of 2:15:0.9:3 to obtain a maleic anhydride-grafted POE pretreatment solution.

[0118] Add a pre-hydrolyzed silane solution to the base material, stir evenly, and then sonicate at 500W for 40 minutes. Add zinc oxide suspension, control the temperature at 60℃, stir at 400rpm, and react for 1.5 hours. Raise the temperature to 70℃, slowly add maleic anhydride-grafted POE pretreatment solution, and then stir for 2 hours. After the reaction is complete, centrifuge at 9000rpm for 30 minutes and collect the solid product. Wash the solid product four times with anhydrous ethanol, and then dry at 70℃ for 14 hours. After drying, grind with a high-speed pulverizer and pass through a 200-mesh sieve to obtain the impact modifier.

[0119] Example 4 Performance Testing

[0120] (I) Using the impact modifiers prepared in Examples 1-3 and Comparative Examples 1-2 as raw materials, polyvinyl chloride (PVC) test samples were prepared. The raw material weight ratio was: 100 parts PVC resin, 8 parts impact modifier, 3 parts calcium-zinc stabilizer, and 2 parts lubricant. The mixture was melt-blended in a twin-screw extruder at a screw speed of 150 r / min and a temperature of 160-180℃. After extrusion granulation, the mixture was injection molded to obtain nano-reinforced impact-resistant PVC test samples. Notched impact strength was tested at 23℃ according to the test method specified in GB / T 1043.1-2008; tensile strength and elongation at break were tested according to the test method specified in GB / T 1040-2018; and flexural strength was tested according to the test method specified in GB / T 9341-2008. Specific test results are shown in Table 1.

[0121] Table 1

[0122]

[0123] As shown in Table 1, the polyvinyl chloride test samples prepared using the nano-reinforced impact modifiers prepared in Examples 1-3 as raw materials achieved a notched impact strength of 64.5-67.2 KJ / m at 23°C. 2 The tensile strength was 66.3-68.6 MPa, the elongation at break was 372-384%, and the flexural strength reached 84.8-87.5 MPa, all of which were significantly enhanced compared to the comparative example. This indicates that the addition of CNC@ACM composite and organo-modified montmorillonite in the nano-reinforced impact modifier of this invention effectively improved the mechanical properties of the polyvinyl chloride test samples.

[0124] (ii) The thermal properties of polyvinyl chloride (PVC) test samples prepared using the impact modifiers prepared in Examples 1-3 and Comparative Examples 1-2 as raw materials were tested. The PVC test samples were heated to 180°C and kept at a constant temperature. The color change time of Congo red test paper was recorded. The Vicat softening point was tested according to the test method specified in GB / T 1633-2000. The specific test results are shown in Table 2.

[0125] Table 2

[0126]

[0127] As shown in Table 2, the PVC test samples prepared using the nano-reinforced impact modifiers prepared in Examples 1-3 as raw materials exhibited a Congo red paper color change time of 82-86 min and a Vicat softening point of 88.1-89.5℃. This demonstrates that the nano-reinforced impact modifiers prepared in this invention have a significant enhancing effect on the thermal properties of the PVC test samples.

[0128] Obviously, there are many other possible implementation methods under the concept of this invention. It should be stated here that any changes made under the inventive concept of this invention will fall within the protection scope of this invention.

Claims

1. A nano-reinforced impact modifier for polyvinyl chloride, characterized in that: The raw material composition by weight is as follows: 55-60 parts of CNC@ACM complex, 6-8 parts of hyperbranched polyglycidyl ether, 6-8 parts of amino-terminated hyperbranched polyamide, 4-6 parts of organo-modified montmorillonite, 4-5 parts of maleic anhydride-grafted POE, 0.6-0.8 parts of silane coupling agent, and 2-3 parts of nano zinc oxide. The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane; The method for preparing the impact modifier includes the following steps: pretreatment of nanocellulose, synthesis of CNC@ACM composite, pretreatment of auxiliary components, preparation of base material, and preparation of nano-reinforced impact modifier. Pretreatment of nanocellulose: Dry nanocellulose is added to toluene at a mass ratio of 1:(19-20) and ultrasonically dispersed for 30-40 min; silanizing agent is added at a mass ratio of (0.3-0.5):1, nitrogen gas is purged, and the temperature is raised to 110-115℃ for 6-8 h; then cooled to room temperature, centrifuged, washed, and dried to obtain silanized nanocellulose; Synthesis of CNC@ACM complex: Silanized cellulose nanoparticles were dispersed in toluene at a mass ratio of 1:(9-10), and sonicated for 30-40 min. After sonication, acrylate rubber was added and stirred until fully dispersed. Then, p-toluenesulfonic acid was added at a mass of 1.5-2% of the cellulose nanoparticles, and the temperature was raised to 110-115℃. The mixture was stirred for 6-7 h. After the reaction was completed, the mixture was cooled to room temperature, and excess ethanol was added and stirred until all the solid precipitated. The solid was then centrifuged, washed, and dried to obtain the CNC@ACM complex. Pretreatment of auxiliary components: Organo-modified montmorillonite is dispersed in deionized water and ultrasonically treated for 20-30 min; then stirred for 10-15 min to obtain an organo-modified montmorillonite dispersion; nano-zinc oxide is added to deionized water at a mass ratio of 1:10, and ultrasonically treated for 20-30 min to obtain a zinc oxide suspension; silane coupling agent, ethanol, and deionized water are mixed at a mass ratio of 1:4:0.2, heated to 40-45℃, and reacted for 30-40 min to obtain a pre-hydrolyzed silane solution; Preparation of base material: Mix CNC@ACM complex with sodium lauryl sulfate and deionized water and stir for 10-15 min; add hyperbranched polyglycidyl ether, heat to 50-55℃, stir and react for 40-50 min, then add amino-terminated hyperbranched polyamide, heat to 60-65℃, and continue to react for 40-50 min to obtain base material; Preparation of nano-reinforced impact modifier: Maleic anhydride-grafted POE was mixed with toluene, sodium lauryl sulfate, and glycerol in a mass ratio of 2:(10-15):(0.8-1):(2.5-3) to obtain a maleic anhydride-grafted POE pretreatment solution; an organic montmorillonite dispersion and a pre-hydrolyzed silane solution were added to the base material and stirred evenly, and then ultrasonically treated for 40-50 min; zinc oxide suspension was added, and the temperature was controlled at 50-60℃, and the reaction was stirred for 1-1.5 h; the temperature was raised to 60-70℃, and the maleic anhydride-grafted POE pretreatment solution was slowly added dropwise, and then the reaction was stirred for 1.5-2 h; after the reaction was completed, the mixture was centrifuged, washed, dried, ground, and passed through a 200-mesh sieve to obtain the nano-reinforced impact modifier.

2. The method for preparing a nano-reinforced impact modifier for polyvinyl chloride according to claim 1, characterized in that: The silanizing agent is a mixture of methyltrimethoxysilane and triethylamine, wherein the triethylamine is 8% of the mass of methyltrimethoxysilane.

3. The method for preparing a nano-reinforced impact modifier for polyvinyl chloride according to claim 1, characterized in that: The mass ratio of the acrylate rubber to the silanized nanocellulose is (6-7):

1.

4. The method for preparing a nano-reinforced impact modifier for polyvinyl chloride according to claim 1, characterized in that: The mass ratio of the CNC@ACM complex, sodium lauryl sulfate, and deionized water is 1:(0.2-0.3):(9-10).

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